The present invention provides novel 2-methoxyimino-2-(pyridinyloxymethyl)phenyl acetamide compounds with (derivatised) hydroxyalkyl substituents on the pyridine ring, their use as fungicidal compounds, and their use in fungicidal compositions comprising at least one of the 2-methoxyimino-2-(pyridinyloxymethyl)phenyl acetamide compounds as the active ingredient.
This invention provides novel 2-methoxyimino-2-(pyridinyloxymethyl)phenyl acetamide compounds of Formula (1), below 
wherein
m is an integer 0-3;
L is xe2x80x94Oxe2x80x94, xe2x80x94CHxe2x80x94, xe2x80x94SOnxe2x80x94, xe2x80x94CH2Oxe2x80x94, xe2x80x94OCH2, xe2x80x94CH2Sxe2x80x94, xe2x80x94SCH2xe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94, or 
wherein n is an integer 0-2;
X, Y, and Z are each independently H, C1-6 alkyl, C1-6 alkoxy, halo-C1-6 alkyl, halo-C1-6 alkoxy, halo, nitro, carbo-C1-6 alkoxy, cyano, C1-6 alkylthio, or halo-C1-6 alkylthio;
W is H, halogen, C1-4 alkyl, C1-4 alkoxy, halo-C1-4 alkyl, or C1-4 alkylthio;
R1 is H, C1-6 alkyl, cycloalkyl, haloalkyl, alkoxyalkyl, alkenyl, alkynyl, haloalkenyl, haloalkynyl, trialkylsilyl, phenyl (optionally substituted by C1-4 alkyl, halo, alkoxy, haloalkyl, or haloalkoxy), benzyl (optionally substituted by C1-4 alkyl, halo, methoxy, haloalkyl, or haloalkoxy), alkylsulphonyl, optionally substituted benzenesulphonyl, trialkylphosphonyl, optionally substituted saturated or unsaturated 5 or 6 membered heterocycle, or xe2x80x94COxe2x80x94R4;
R2 is H, alkyl (optionally, a C1-C6 alkyl), cycloalkyl, phenyl (optionally substituted by C1-4 alkyl, halo, alkoxy, haloalkyl, haloalkoxy, alkoxycarbonyl, alkylcarbonyl, arylcarbonyl, or aryloxy), hydroxyalkyl, optionally substituted heterocycle, haloalkyl, optionally substituted naphthyl, or xe2x80x94CH2OR5;
R3 is H, alkyl (optionally, a C1-C6 alkyl), cycloalkyl, phenyl (optionally substituted by C1-4 alkyl, halo, alkoxy, haloalkyl, haloalkoxy, alkoxycarbonyl, alkylcarbonyl, arylcarbonyl, or aryloxy), hydroxyalkyl, optionally substituted heterocycle, haloalkyl, optionally substituted naphthyl or xe2x80x94CH2OR5;
or R1 and R2 together form a link of 1-3 atoms which form an optionally substituted heterocyclic ring containing one or more oxygen atoms;
or R2 and R3 together form an optionally substituted carbocyclic or heterocyclic ring;
R4 is H, C1-6 alkyl, cycloalkyl, haloalkyl, alkoxyalkyl, alkenyl, alkynyl, haloalkenyl, haloalkynyl, phenyl (optionally substituted by C1-4 alkyl, halo, methoxy, haloalkyl, haloalkoxy), benzyl (optionally substituted by C1-4 alkyl, halo, methoxy, haloalkyl, or haloalkoxy), alkoxy, or dialkylamino; and
R5 is alkyl (optionally, a C1-C6 alkyl), alkanoyl, optionally substituted benzoyl, alkylsulphonyl, or optionally substituted benzenesulphonyl.
The present invention also provides compositions comprising one or more compounds of Formula (1) in combination with phytologically-acceptable carriers and/or diluents. Methods for the use of compounds of Formula (1) and compositions comprising one or more compounds of Formula (1) are also provided.
Throughout this document, all temperatures are given in degrees Celsius and all percentages are weight percentages, unless otherwise stated.
The term xe2x80x9chalogenxe2x80x9d or xe2x80x9chaloxe2x80x9d refers to F, Cl, I, or Br.
The term xe2x80x9calkylxe2x80x9d, xe2x80x9calkenylxe2x80x9d, or xe2x80x9calkynylxe2x80x9d refers to a straight chain or branched chain carbon radical containing the designated number of carbon atoms.
The term xe2x80x9calkoxyxe2x80x9d refers to a straight or branched chain alkoxy group.
The term xe2x80x9chalo alkylxe2x80x9d refers to a straight or branched alkyl group substituted with one or more halo atoms. The term xe2x80x9chalo alkoxyxe2x80x9d refers to an alkoxy group substituted with one or more halo atoms.
The term xe2x80x9carylxe2x80x9d or xe2x80x9cPhxe2x80x9d refers to a phenyl group. The term xe2x80x9csubstituted arylxe2x80x9d refers to a phenyl group substituted with C12-C6 alkyl, C1-C6 alkoxy, halo-C1-C6 alkyl, halo-C1-C6 alkoxy, halo, nitro, carbo-C1-C6 alkoxy, or cyano. The term xe2x80x9cheteroarylxe2x80x9d refers to pyridyl, pyridinyl, pyrazinyl or pyridazinyl.
The term xe2x80x9cMexe2x80x9d refers to a methyl group. The term xe2x80x9cEtxe2x80x9d refers to an ethyl group. The term xe2x80x9cPrxe2x80x9d refers to a propyl group. The term xe2x80x9cBuxe2x80x9d refers to a butyl group.
The term xe2x80x9cEtOAcxe2x80x9d refers to ethyl acetate.
The term xe2x80x9cppmxe2x80x9d refers to parts per million. The term, xe2x80x9cpsixe2x80x9d refers to pounds per square inch.
The term xe2x80x9cM.P.xe2x80x9d refers to melting point. The term xe2x80x9cbpxe2x80x9d refers to boiling point.
While all the compounds of this invention have fungicidal activity, certain classes of compounds may be preferred for reasons such as, for example, greater efficacy or ease of synthesis.
A preferred class includes those compounds of Formula (2), below 
wherein the substituents are as defined in Formula (1), above.
A more preferred class includes those compounds of formula (3), below 
wherein the substituents are as defined in Formula (1), above.
A next more preferred class includes those compounds of Formula (4), below 
wherein the substituents are as defined in Formula (1), above.
A next more preferred class includes those compounds of Formula (5), below 
wherein the substituents are as defined in Formula (1), above.
A next more preferred class includes those compounds of formula (6), below 
wherein X is methyl, halo, or haloalkyl and the additional substituents are as defined in Formula (1), above.
Currently, it is sometimes preferred when R1 is hydrogen, C1-4 alkyl, formyl, alkanoyl, alkoxycarbonyl, dialkylaminocarbonyl, or dialkylphosphonyl and R5 is H, C1-4 alkyl.
Compounds of the present invention may be prepared by routes commonly known in the art using commercially available or readily synthesized starting materials. Such general procedures are described in Scheme 1 and Scheme 2, below, wherein the substituents are as described in Formula (1), above, and V is a leaving group, such as, for example, F, Cl, or SO2CH3. 
An compound of Formula (8) is reacted with an appropriately substituted pyridine derivative of Formula (7) in the presence of a base in an aprotic solvent. Examples of an appropriate solvent for this reaction would include, but are not restricted to, tetrahydrofuran, dimethyl sulphoxide, acetone, acetonitrile, dimethyl formamide, or N-methylpyrrolidinone. Examples of an appropriate base for this reaction would include, but are not restricted to, sodium hydride, potassium hydride, potassium carbonate, potassium t-butoxide, or a tertiary amine derivative such as triethylamine. 
A ketone derivative of Formula (9) is reacted with an organometallic reagent of the form R3xe2x80x94M in a compatible solvent to give an alcohol of the Formula (10). Examples of a group R3xe2x80x94M would include, but are not restricted to a Grignard reagent such as methyl magnesium bromide, an organolithium reagent such as phenyl lithium or a hydride transfer reagent such as sodium borohydride. Examples of a suitable solvent would be tetrahydrofuran, diethyl ether, or an appropriate alcohol, selected by compatibility with the reagent and the transformation being carried out. The compound of Formula (10) may be further derivatised by reaction with an appropriate alkylating or acylating reagent R1xe2x80x94Q, optionally in the presence of an appropriate base. Compounds of the Formula R1xe2x80x94Q would include, but are not restricted to acetic anhydride, benzyl bromide, dimethyl carbamoyl chloride, ethyl chloroformate, diethyl phosphoryl chloride, 5-chloro-3-methyl-2-methylsulphonylpyridine. Examples of a suitable base would include, but are not restricted to a tertiary amine such as triethylamine or pyridine, sodium carbonate, sodium hydride, potassium hydride, or potassium t-butoxide. 
A compound of Formula (10) may also be reacted with a sulphonyl chloride of the formula RSO2Cl) in the presence of a suitable base in a compatible solvent to give the corresponding chloride of Formula (11). Examples of a suitable sulphonyl chloride would be methanesulphonyl chloride, p-toluenesulphonyl chloride, and examples of a suitable base would be pyridine, triethylamine, or Hxc3xcnig""s base. The compound of formula (11) may be reacted further with a metal alkoxide salt in a compatible solvent to give a compound of Formula (1). Examples of a suitable metal alkoxide would include sodium methoxide, potassium ethoxide, or magnesium methoxide produced in situ by the addition of magnesium metal to methanol.
The following examples further illustrate this invention. The examples should not be construed as limiting the invention in any manner.